Resinous copolymers of 4-methylene-1, 3-dioxolane



?atented eb. 11, 1947 RESINOUS COPOLYMERS F 4-METHYLENE- 1,3-DIOXOLANE William 0. Kenyon and Thomas F. Murray, In, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester,

New Jersey N. Y., a corporation or No Drawing. Application August 15, 1942, I

Serial No. 454,906

12 Claims. (oi. zoo-as) This invention relates to resinous polymers and pounds.

Monomeric 4-methylene-L3-dioxolanes having the following general formula:

H.c=o---cm wherein R and R each represents hydrogen, an alkyl group or an aryl group can be prepared by the method of H. O. L. Fischer et al., Ber. 63B, 1732 to 1744 (1930). Attempts to homopoly'merize such monomers wherein R represents hydrogen and R represents an alwl group have failed.

We have now found that 4-methylene-L3-dloxolanes can be copolymerized with other unsaturated organic compounds to yield useful resinous materials. Moreover, we have found that 4- methylene-2-phenyl-1,3-dioxolanes, as well as other 2-aryl-4-methylene-1,3-dioxolanes can be homopolymerized. It is, accordingly, an object of our invention to provide new resinous polymers and to provide a process for preparing the same. Other objects will become apparent hereinafter.

In accordance with our invention, we copolymerize a it-methylene-1,3-dioxolane with an unsaturated organic compound, especially an unsaturated organic compound containing a carbon-to-carbon double bond conjugated with a carbon-to-oxygen double bond, such as u-methylene carboxylic acids and their esters, vinyl ketones and anhydrides of ethylene-1,2-carboxylic acids (1. e. anhydrides of 1,2-dicarboxyethylenes) With many of such unsaturated organic compounds, the 4-methylene-1,3-dioxolanes copolymerize very rapidly without the application of external heating and without a catalyst. In fact, in some instances a diluent for the reactants, e. g. 1,4-dioxane, and/or external cooling may be necessary to moderate the violence of the reaction. With some of the other unsaturated compounds, the polymerization is advantageously accelerated by heating or by the use of catalysts, such as the catalysts which are known to eifect the polymerization of organic compounds containing a group, e. g. organic peroxides such as benzoyl peroxide, acetyl benzoyl peroxide, etc.

The following examples will serve to illustrate our new resinous polymers and the process for I preparing the same.

Example 1.--C0polymer of 2-methyl-4-methylene-1,3-diozrolane and a-methacrylic acid 5 g. of 2-methyl-4-methylene-1,3-dloxolane and 5 g. of e-methacrylic acid were mixed. The

mixture warmed spontaneously and became hard. The hard product was brilliant, clear and colorless. It was dissolved in a. mixture of acetone and water and precipitated by pouring the solution into a mixture of two volumes acetone and one volume of diethyl ether. The product was flocculent when precipitated but became sticky when brought from the precipitating liquid into the air. It was dried at 0., giving a brittle, glossy, colorless material. The material was analyzed for carbon and hydrogen and found to contain 54.66 percent by weight, of carbon and 7.69 percent of hydrogen. A similar product was dissolved in water and titrated with standard sodiu-m hydroxide. It was found to contain 66.5 percent of a-methacrylic acid. From these results it appeared that some acetaldehyde was split ofi from the dioxolane during polymerization, and

that the copolymer contained u-methacrylic acid 66.5 percent,'dioxo lane compound 11.4 percent and the corresponding dialcohol 22.1 percent.

Varying the proportion of the monomers used affects the type of copolymer obtained with amethacrylic acid. Below are given the results obtained when the ratio of the monomers was changed. No catalyst was used in the polymerizations.

ene-1,3-dioxolane. and maleic anhydride 1 When 2- methyl 4 methylene-1,3-dioxolane and maleic anhydride were mixed, they reacted violently, giving off considerable heat and producing a dark polymer. The reaction can be 2,41s,ose

3 modified by carrying it out in a diluent, such as acetone or preferably 1,4-dioxane.

25 groi maleic anhydride were dissolved in 50 g. of dry 1,4-dioxane. 25 g. of 2-methyl-4-methylene-l',3-dioxolane were added to'the solution. Reaction began with external heating and was modified by slight warming or cooling, as required, by running waterover the flask in which the reaction was being carried out. when the reaction mixture has become quite viscous, it was warmed on a steam bath for V2 hour. At the end 01 this time, the reaction mixture was very viscous, clear and substantially colorless. It was diluted with 1,4-dioxane and the resinous copolymer was precipitated by pouring the dioxane mixture into benzene. The precipitated copolymer was dried at 50 to 60 C. and found to contain 53.43 percent of carbon and 5 percent of hydrogen. These values agree well with the calculated values 0! 54.5 percent oi! carbon and 5.06

percent of hydrogen in a copolymer containing I equimolecular proportions of maleic anhydride and the dioxolane.

Example 3.401102 of z-methyz-r-memyzene-1,3-diozolane and methyl -methacrylate A mixture was made of 4 g. or 2-methyl-4- methylene-1,3-dioxolane, 16 g. of methyl a-methacrylate and 0.2 g. of benzoyl peroxide. The vessel containing the mixture was closed and maintained at 60 C. for 24 hours. A hard clear. colorless copolymer resulted. The copolymer was dissolved in acetone and precipitated by pouring the acetone solution into water. Although the dioxolane in the starting reaction mixture was equal to 20 percent by weight of reaction mixture, the copolymer contained only 6.05 percent combined dioxolane.

mixture, the copolymer contained 4.6 percent and contained 11.25 percent combined dioxolane.

- A series of these copolymers of 2-methyl-4- methylene-1,3-dioxolane and methyl, a-methacrylate were compressionmolded and the physical properties of the molded products compared.

Ratio of dioxolane to methyl e-methacrylate in starting reaction mixture /90 /85 Impact strength--- 9.16 4.64 3.90 2.69 Hardness:

Shore 83.8 86.0 84.0 64.8 Rockwell 107.6 100.4 91.6 27.6 Elongation, percent 4.33 4.00 7.66 3.66 Strength: Tensile 7,100, 4,820 6,060 1,440 Flexural 14,920 8,180 9,590 1,015

When 10 percent of the di-- oxolane was employed in the starting reaction when 40 percent of the dioxolane was employed I 'in-the starting reaction mixture, the copolymer flux condenser.

Example 4.Copolymer of 2-methyl-4-methylene-L3-diozcolane and acrylic acid 10 g. of acrylic acid were dissolved in 20 g. of dry 1,4-dioxane. To the solution were added 10 g. of 2-methyl-4-methylene-1,3-dioxolane. The mixture was heated in a 60 C. bath under a re- Inabout A; hour the reaction mixture had become a viscous solution. Heating was continued for about 3 additional hours. The reaction mixture was then diluted with 1,4-dioxane and the copolymer precipitated by pouring the dioxane solution into carbon tetrachloride.

Example 5.--C0pol'ymer of Z-methyZ-si-methylene-L3-dioxolane 6nd methyl acrylate A mixture was made of 25 g.'oif 2-methyl-4- methylene-1,3-dioxolane, 25 g. of methyl acrylate and 0.5 g. of benzoyl peroxide. The mixture was warmed under reflux at 60 C. for about 6 hours and then cooled. Polymerization was. very imtligh. The resulting polymer was very soft and .Emmple 6.-Copolymer of 2-methyl-4-methylene-LS-dlomolane and methyl vinyl ketone A mixture of equal parts of 2-methyl-4-methylene-LB-dioxolane and methyl vinyl ketone gave a soft, polymer in about '12 hours, warming at 60 C. with no catalyst.

Example 7.Copolymer of 2-me'thyl-4-methylene-1,3-dl0:rolane, vinyl acetate and e-methacrylic acid A solid, though soft, copolymer was obtained when a mixture of 5 g. of 2-methyl-4-mthylene- 1,3-dioxolane, 5 g. of vinyl acetate and 1 g. of methacrylic acid were kept at 60 C. for 24 hours. No catalyst was used.

Example 8.C'opolymer of 4-methylene-,1,3-diozcolane and a-methacrylic acid 5 g. of 4-methylene-1,3-dioxolane and 5 g. of methacrylicacid were mixed. 'Aiter one hour standing at20 to 25 C., no significant polymerization had occurred. The. mixture was then placed in an oven at 60 C. and allowed to stand at this temperature 12 to 15 hours. A solid, hard, clear, bubble-free resinous copolymer was obtained.

Example 9.Copolymer of 4-methylene-L3-dioxolane and methyl a-methacrylate I 37.5 g. "of 4-methylene-l,3-dioxolane and 87.5 g. of methyl a-methacrylate and 1.0 g. of benzoyl peroxide were mixed and the mixture heated in a hot water bath at 40 C. After 48 hours a hard, clear, colorless resinous copolymer was obtained. The copolymer did not retain its shape well upon molding.

Example 10.-C'opolymer of 2- (n-DT MIZ) -4- methylene-1,3-diorolane and a-metham-ylic acid 6.4 g. of 2-(n-propyl)-4-methylene-1,3 dioxolane and 4.3 g. of a-methacrylicacid were mixed.

0.1 g. of benzoyl peroxide was added to the mixture. The mixture was then heated at 50 to 60 C. and in less than one hour polymerized to give a somewhat opaque, hard, plastic mass which swelled considerably, but did not dissolve in 10 percent aqueous sodium hydroxide. A similar procedure, without, catalyst, gave a similar res- .7-

inous product.

Erdmple" '11.--C'o)olymer of z-phenuld-methfllene-1,3-dioa:olane and a-methacrylic acid 8 g. of 2-phenyl- 4-methy1ene!l,3-dioxolane and 4.3 g. of a-methacrylic acid were mixed. Polymerization occurred spontaneously at 20 to 25 C.

in a few minutes to give a slightly cloudy, slightly soft resinous copolymer which became hard in about 72 hours. The copolymer was. soluble in acetone but practically insoluble in percent aqueous sodium hydroxide, although it swelled somein this reagent and turnedreddish brown.

Example 12.--Cop0l ymer of 2,2-dim'ethyl-4- methylene-1,3-dioxolane and 'maleic' "anhydn'de Equimolecular. proportions of 2,2-dimethyl-4- methylene-1,3-dioxolane and malelc'anhydride reacted so vigorously that it was necessary to coolxthe mixture to controt the polymerization. At the end of one hour at 20 to 25 C., the polymerization product was too viscous to flow and I olane and and 4.3 .g. (an equimolecular proporwere-employed in equimolecular -proportion-,'-and if combined in equimolecular proportion the'calculated carbon and hydrogen contents oi" the copolymers would be 61.9 percent and 6.34-percent respectively. The analytical values obtained were 61.4 percent of carbon and 6.24 percentof hydrogen.

Example 17.-C'opolymerof methylene 1,3 dioxolane and as g. or '2-(m-tolyl)-4-methylene-1,3-diox- -2 (wt-total) -4'- a methacrilli'c tlon) or a-methacryli'c acid were mixed. The

upon further standing at 20 to C. an opaque resinous copolymer obtained; Example 1 3.Copolym'er oj '2-phenyl-4-qnethylene-1,3"-dio3:olane and maleic anhydride Equimolecular proportions of 2-phenyl 4- methylene-1,3-dioxolane and maleic anhydride reacted vigorously as in the preceding Example 12 with'simll'ar results. Example 14. Copolymer of v;--meth.ulene-1,4-

diozaspiro [4.5] decane and a-methacrylie acid v 7.8 g. of 2-methylene-l,4-dloxaspiro [4.51

decane and 4.3 g. of a-metha'crylic acidwere mixed and the mixture heated in an oven at 50 to 60 C. 24 hours later, a, hard copolymer had formed which was clear except for a small opaque area'inthe center of the'reaction mass. On further standing this opaque area disappeared, yielding a perfectly clear yellow material which was soluble in acetone, but only partly soluble in aqueous 10 percent alkali. I

Example 15.-Copolymer of z-methylene-L4-dioxaspiro [4.5] decane and methyl a-methacrylate 7.8 g. of 2-methylene-L4-dioxaspiro [4.5] decane were mixed with 5 g. of methyl (r-methacrylate. 0.13 g. of benzoyl peroxide were added to the mixture. The resulting mixture was heattemperature ro'se spontaneously, and in a few minutes the mixture was was allowed to stand'at 20 to 25 C; for '72 hours,

whereupon a hard, clear, colorless copolymer was equimolecularproportions of combined; dioxolane and a-methacrylic'acid'.

Example 18.--Copolymer of 2- (p-chlorophenyl) anethylene-Lii-dioxolane and wmmacrylic 8.8 g. or 2-(p-chlorophenyl).-4-methylene 1,3-

dioxolane vand 4:3 g. of methacrylic acid: were mixed and themixture heatedin an oven at to C.-. :At the end of four days. aclear. hard,

. colorless copolymer had formed.

Example 19.-'cocozymer of 2-methyl-4-methylene-1,3-dio:rolane and methynsoproo nul Ice- 5 g. oi 2-methyl-4-methylene-1,3-dioxolane were mixed with 5 g. of methyl isopropenyl ketone. The mixture was allowed to stand at 20 to 25 C. for 72 hours with no apparent change.

0.1 g. of benzoyl peroxide catalyst was added to the mixture, and after it had dissolved, the resuiting. solution was placed in an oven at 60 C. Twenty-five days later, a hazy copolymer had formed. The copolymer was dissolved in acetone ed at 50 to 60 C. for 24 hours. A soft copolymer resulted which was dissolved in acetone. The acetone solution was poured into water to precipitate the copolymer which was dried at 50to 60C. Analysis showed a carbon content of 64.4 percent and a hydrogen content of 8.3 percent. This carbon content indicated that the copolymer contained 58 percent of combined methyl methacrylate. Two

methoxyl determinations showed an average value of 16 percent for methoxyl content, indicating that the copolymer contained 54 percent combined methyl a-methacrylate.

Example 16.Copolym er of Z-methylene-lA-diozraspz'ro [4.5] decane and maleic anhydride 7.8 g. of 2-methylene-1,4-dioxaspiro14.5] Y

decane were mixed with 5 g. of maleic anhydride. The mixture polymerized spontaneously and produced a yellowish brown polymer. This was dissolved in acetone. The copolymer was precipitated by pouring the acetone solution into diethyl ether. The resin was filtered ofi, washed with diethyl ether and dried. The two monomers and precipitated by pouring the acetone solution into water. After drying the copolymer was found to contain 68.2 percent ofcarbon and 9.14

percent of hydrogen which indicated that about '72 percent of the copolymer was combined isopropenylketpne and the remainder combined dioxolane.

Example 20.--Ho1'nopo lymer of 2-phenyl-4- I methylene-1,3-dioxolane 10 g; of 2-phenyl-4 methylene-1,3-dioxolane were mixed with 0.1 g. of benzoyl peroxide. The

mixture was heated at 50 to 60 C. for 48 hours. I 'I'he homopolymer .which formed was hard and clear. It was soluble in acetone and precipitated when the acetone solution was poured into water.

Example 21.-Hom0polymer of 2,2-dimethyl-4- methylene-1,3- dioarolane 5.7 g. of 2,2Fdixnethyl-4-methylene-1,3-dioxolane polymerized in a very few minutes at 20 to 25 C. with catalyst, to give an opaque solid which became clear upon standing for 72 hours. Thetoo viscous to flow. It

Some water distilled over with the 4-methylene- 1,3- dioxolane. Water was separated of! and the dioxolane washed with distilled water and then dried over potassium carbonate. Thedioxolane was redistilled through a column packed with copper helices. The boiling point was 87.5 C.

The dioxolane described in Example 23 and utilized in Examples 15, 16 and 22 is a spiro compound since it contains one and only one carbon atom common to two ring systems and hence cannot be conveniently named in the same manner as the other dioxolanes. However, since the spiro compound is clearly a dioxolane of the same category as the other 4-methylene-1,3-dioxolanes, it is intended to come under the generic term "a 4-methylene-1,3rdioxolane."

What we claim as our invention and desire to be secured by Letters Patent of the United States is:

1. A process for preparing a resinous copolymer comprising polymerizing a mixture of 2-methyl- 4-methylene-1,3-dioxolane with methyl methacrylate, said mixture containing about 10 per cent by weight of 2-methyl-4-methylene-1,3 dioxolane.

2. A process for preparing a resinous copolymer comprising polymerizing a mixture of about equal parts by weight of maleic anhydride and a 4- methylene-1,3-dioxolane.

3. A- process for preparing a resinous copolymer comprising polymerizing a mixture of about equal parts by weight of maleicanhydride and 2-meth- 'yl-4-methylene-1,3-dioxolane. I v

4. A process for preparing a resinous copolymer comprising polymerizing a mixture of about equal parts by weight of methyl isopropenyl ketone and- 2-methyl-4-methylene-1,3dioxolane.

5. A process for preparing a resinous copolymer comprising polymerizing a mixture of a 4-methylene-1,3-dioxolane and another unsaturated organic compound selected from the group consisting of acrylic acid, u-methacrylic acid, maleic anhydride, methyl vinyl ketone, methyl isopro- Penyl ketone, vinyl acetate, methyl acrylate and esters of a-methacrylic acid and an alcohol of the formula CnH2n+1OH-Wh8I6iH n represents a positive integer of from 1 to 4, the dioxolane constituting from 10 to 99 per cent by weight of the mixture. 6. A process for preparing a resinous copolymer comprising polymerizing,- in the presence of an organic peroxide, a mixture of a 4-methylene- 1,3-dioxolane and another unsaturated organic compound selected from the group consisting of acrylic acid, a-methacrylic acid, maleic anhydride, methyl vinyl ketone, methyl isopropenyl ketone, vinyl acetate, methyl acrylate and esters of a-methacrylic acid and an alcohol 0! the for-' mula Cali-+1011? wherein n represents a positive integer of from 1 to 4, the dioxolane constituting from 10 to 90 per cent by weight of the mixture.

7. A resinous copolymer obtained by the process of claim 5. I

8. A resinous copolymer obtained by the process of claim 6.

9. A resinous copolymer obtained by the process of claim 1. 1

'10. A resinous copolymer obtained by the process of claim 2.

11. A resinous copolymer obtained by the process of claim 3.

12. 'A resinous copolymer obtained by the process of claim 4.

, WILLIAM O. KEN'YON. .THOMAS F. MURRAY, JR.

REFERENCES crrEn The following references are of record in the file of this patent:

UNITED STATES PA'I'EN'TS Number Name Date 2,098,108 Reppe Nov. ,2, 193'! 2,088,577 Conaway Aug. 3; 1937 v FOREIGN PATENTS:

' Number Country Date 339,882 British Dec. 18, 1930 340,008 British Dec. 19, 1930 487,604 British June 22, 1938 o'rma REFERENCES Fischer et al.: Ber. 633, 1732-44 (1930 Chemical Abstracts, vol. 24, page 5024 (1930).

Whelan: J; Amer. Chem. 800., vol. 51, pages 3115-23 (1929). I I Richter-Spielman, Organic Chemistry, vol. I,

2nd. .ed., pages 492 and 507. 1

Chemical Abstracts, vol. 23, page 5468 (1929). 

